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Acta Cryst. (2007). E63, o3974    [ doi:10.1107/S1600536807042067 ]

A new polymorph of 2'-(4-methoxybenzylidene)isonicotinohydrazide monohydrate

M. Lin and S.-X. Liu

Abstract top

The title compound, C14H13N3O2·H2O, is a new orthorhombic polymorph of a structure reported previously [Jing, Fan, Yu, Chen & Deng (2005). Acta Cryst. E61, o3208-o3209]. The crystal structure is stabilized by a network of N-H...O and O-H...N hydrogen bonds linking three molecules to each water molecule, forming layers in the bc plane.

Comment top

As part of a study of substituted isonicotinohydrazides and their complexes, a new polymorph of 2'-(4-Methoxybenzylidene)isonicotinohydrazide monohydrate, I, was synthesized in our group and its structure is reported here, Fig. 1. A polymorph of this molecule II has also been reported (Jing et al., 2005) and the two compounds show similar molecular configurations, bond lengths and angles. In I, the system (C7–C14/N2/N3/O2) is planar, the r.m.s. deviation of fitted atoms being 0.0481 Å, and the pyridine ring(C1–C6/N1) is also planar with an r.m.s. deviation of 0.0059 Å. The dihedral angle between the two planes is 43.20 (9)°, while the corresponding angle in polymorph II is 36.78 (3)°.

There are three hydrogen bonds for every solvent water molecule in the crystal structure, Table 1. These link the molecules of I and the water solvate into layers in the bc plane, Fig 2.

Related literature top

For a polymorph of the title compound, see: Jing et al. (2005). For other isonicotinohydrazide derivatives, see: Maurya et al. (2005); Qiu et al. (2006); Yang et al. (2006); Yin et al. (2005); Yin et al. (2005).

Experimental top

Pyridine-4-carboxylic acid hydrazide (10 mmol, 1.37 g) was dissolved in anhydrous ethanol (10 ml) and the mixture was stirred for several minutes at 351 K. 4-methoxybenzaldehyde (10 mmol, 1.36 g) in ethanol (10 ml) was added dropwise and the mixture refluxed for 3 h. The solid product was filtered off and recrystallized from a methanol solution. Single crystals of (I) were obtained after 7 d.

Refinement top

The H Atoms in water molecule were located in a difference Fourier maps, and then allowed to ride on the oxygen atom with Ueq = 1.5Ueq(O). The other H atoms were placed in idealized positions and treated as riding with C—H = 0.93 Å, Uiso = 1.2Ueq(C) for aromatic 0.96\ %A, Uiso = 1.5Ueq(C) for CH3 atoms and 0.86 Å, Uiso = 1.2Ueq(O) for the NH groups.

In the absence of significant anomalous scattering effects, Friedel pairs were merged.

Computing details top

Data collection: TEXRAY (Molecular Structure Corporation, 1999); cell refinement: TEXRAY (Molecular Structure Corporation, 1999); data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with the atom-numbering scheme and 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. A plot illustrating extended three-dimensional structure of (I), hydrogen bonds are drawn as dashed lines. H atoms not-involved in hydrogen bonding have been omitted.
2'-(4-methoxybenzylidene)isonicotinohydrazide monohydrate top
Crystal data top
C14H13N3O2·H2OF000 = 576
Mr = 273.29Dx = 1.343 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 12498 reflections
a = 7.415 (5) Åθ = 3.1–27.5º
b = 12.621 (8) ŵ = 0.10 mm−1
c = 14.4387 (13) ÅT = 293 (2) K
V = 1351.1 (13) Å3Prism, colourless
Z = 40.40 × 0.30 × 0.25 mm
Data collection top
Rigaku R-AXIS RAPID imaging-plate
diffractometer		1768 independent reflections
Radiation source: fine-focus sealed tube1130 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.075
T = 293(2) Kθmax = 27.5º
ω scansθmin = 3.1º
Absorption correction: ψ scan
(TEXRAY; Molecular Structure Corporation, 1999)		h = −9→9
Tmin = 0.962, Tmax = 0.976k = −15→16
12498 measured reflectionsl = −18→18
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.062P)2]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.051(Δ/σ)max < 0.001
wR(F2) = 0.136Δρmax = 0.21 e Å−3
S = 1.09Δρmin = −0.22 e Å−3
1768 reflectionsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
183 parametersExtinction coefficient: 0.010 (3)
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
Crystal data top
C14H13N3O2·H2OV = 1351.1 (13) Å3
Mr = 273.29Z = 4
Orthorhombic, P212121Mo Kα
a = 7.415 (5) ŵ = 0.10 mm−1
b = 12.621 (8) ÅT = 293 (2) K
c = 14.4387 (13) Å0.40 × 0.30 × 0.25 mm
Data collection top
Rigaku R-AXIS RAPID imaging-plate
diffractometer		1768 independent reflections
Absorption correction: ψ scan
(TEXRAY; Molecular Structure Corporation, 1999)		1130 reflections with I > 2σ(I)
Tmin = 0.962, Tmax = 0.976Rint = 0.075
12498 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.051Δρmax = 0.21 e Å−3
wR(F2) = 0.136Δρmin = −0.22 e Å−3
S = 1.09Absolute structure: ?
1768 reflectionsFlack parameter: ?
183 parametersRogers parameter: ?
H-atom parameters constrained
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R– factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.1918 (4)0.3865 (3)0.0147 (2)0.0568 (8)
N20.1289 (5)0.2584 (2)0.34455 (19)0.0499 (7)
H2B0.15060.32540.34410.060*
N30.1091 (4)0.2054 (2)0.42850 (18)0.0499 (7)
O10.0859 (4)0.10855 (18)0.25897 (17)0.0588 (7)
O20.1211 (4)0.1269 (2)0.87090 (17)0.0633 (7)
C10.0711 (5)0.3734 (3)0.1690 (2)0.0464 (8)
H1A0.00830.40500.21740.056*
C20.1005 (5)0.4270 (3)0.0870 (3)0.0538 (9)
H2A0.05430.49520.08150.065*
C30.2553 (6)0.2881 (3)0.0242 (3)0.0593 (10)
H3A0.31930.2587−0.02490.071*
C40.2308 (6)0.2268 (3)0.1036 (2)0.0553 (10)
H4A0.27580.15810.10680.066*
C50.1382 (5)0.2703 (2)0.1774 (2)0.0432 (8)
C60.1143 (5)0.2054 (3)0.2645 (2)0.0453 (8)
C70.1430 (5)0.2620 (3)0.4997 (3)0.0519 (9)
H7A0.17590.33240.49100.062*
C80.1328 (5)0.2214 (3)0.5944 (2)0.0481 (8)
C90.0858 (6)0.1177 (3)0.6160 (2)0.0585 (10)
H9A0.05800.07070.56850.070*
C100.0795 (6)0.0829 (3)0.7076 (3)0.0589 (10)
H10A0.04890.01300.72080.071*
C110.1190 (5)0.1526 (3)0.7790 (2)0.0494 (9)
C120.1615 (6)0.2564 (3)0.7585 (3)0.0578 (10)
H12A0.18400.30400.80630.069*
C130.1708 (5)0.2900 (3)0.6680 (3)0.0568 (10)
H13A0.20290.35980.65550.068*
C140.0980 (7)0.0184 (3)0.8971 (3)0.0709 (12)
H14A0.10910.01200.96310.106*
H14B0.1886−0.02410.86750.106*
H14C−0.0194−0.00540.87820.106*
O30.1336 (5)0.4908 (2)0.3704 (2)0.0803 (10)
H3WB0.04220.53130.33910.121*
H3WA0.20550.53230.41530.121*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.071 (2)0.066 (2)0.0328 (16)−0.0101 (18)0.0001 (14)0.0050 (15)
N20.0706 (19)0.0437 (14)0.0354 (16)−0.0038 (15)−0.0052 (15)0.0037 (11)
N30.0684 (19)0.0549 (16)0.0263 (14)0.0020 (17)−0.0028 (14)0.0058 (12)
O10.0901 (19)0.0451 (13)0.0413 (15)−0.0018 (14)−0.0058 (14)0.0007 (10)
O20.0882 (19)0.0667 (16)0.0350 (14)0.0010 (17)−0.0002 (14)0.0037 (12)
C10.0572 (19)0.0500 (18)0.0321 (17)−0.0063 (17)−0.0004 (16)−0.0049 (15)
C20.064 (2)0.0531 (19)0.044 (2)−0.0012 (19)−0.0031 (19)0.0052 (16)
C30.068 (2)0.073 (3)0.038 (2)−0.002 (2)0.0084 (18)−0.0040 (19)
C40.069 (2)0.053 (2)0.043 (2)0.0079 (19)−0.0014 (18)−0.0059 (16)
C50.0503 (17)0.0480 (18)0.0314 (17)−0.0069 (17)−0.0030 (15)0.0015 (14)
C60.058 (2)0.0463 (17)0.0313 (18)0.0036 (18)−0.0044 (17)−0.0003 (14)
C70.062 (2)0.0528 (19)0.0412 (19)0.0022 (19)−0.0040 (17)0.0019 (14)
C80.057 (2)0.0530 (19)0.0342 (18)0.0043 (19)−0.0057 (16)0.0033 (14)
C90.081 (3)0.055 (2)0.040 (2)−0.004 (2)−0.008 (2)−0.0054 (16)
C100.083 (3)0.0517 (19)0.042 (2)−0.005 (2)−0.002 (2)−0.0010 (16)
C110.053 (2)0.058 (2)0.0368 (19)0.0042 (18)0.0012 (16)0.0037 (15)
C120.079 (3)0.056 (2)0.038 (2)0.000 (2)−0.0064 (19)−0.0045 (17)
C130.074 (2)0.0494 (19)0.047 (2)−0.0031 (19)−0.0084 (19)−0.0005 (18)
C140.092 (3)0.070 (3)0.050 (3)0.006 (3)0.015 (2)0.0141 (19)
O30.119 (3)0.0526 (14)0.070 (2)0.0047 (18)−0.037 (2)−0.0100 (13)
Geometric parameters (Å, °) top
N1—C31.335 (5)C7—C81.461 (5)
N1—C21.345 (5)C7—H7A0.9300
N2—C61.341 (4)C8—C91.389 (5)
N2—N31.392 (4)C8—C131.401 (5)
N2—H2B0.8600C9—C101.395 (5)
N3—C71.277 (5)C9—H9A0.9300
O1—C61.242 (4)C10—C111.386 (5)
O2—C111.367 (4)C10—H10A0.9300
O2—C141.430 (5)C11—C121.379 (5)
C1—C21.380 (5)C12—C131.376 (5)
C1—C51.398 (5)C12—H12A0.9300
C1—H1A0.9300C13—H13A0.9300
C2—H2A0.9300C14—H14A0.9600
C3—C41.395 (5)C14—H14B0.9600
C3—H3A0.9300C14—H14C0.9600
C4—C51.381 (5)O3—H3WB0.9612
C4—H4A0.9300O3—H3WA0.9891
C5—C61.512 (5)
C3—N1—C2116.9 (3)C8—C7—H7A118.4
C6—N2—N3120.1 (3)C9—C8—C13117.5 (3)
C6—N2—H2B119.9C9—C8—C7123.6 (3)
N3—N2—H2B119.9C13—C8—C7118.8 (3)
C7—N3—N2114.3 (3)C8—C9—C10121.3 (3)
C11—O2—C14118.9 (3)C8—C9—H9A119.4
C2—C1—C5118.3 (3)C10—C9—H9A119.4
C2—C1—H1A120.8C11—C10—C9119.8 (3)
C5—C1—H1A120.8C11—C10—H10A120.1
N1—C2—C1123.9 (3)C9—C10—H10A120.1
N1—C2—H2A118.0O2—C11—C12115.5 (3)
C1—C2—H2A118.0O2—C11—C10125.0 (3)
N1—C3—C4123.6 (3)C12—C11—C10119.5 (3)
N1—C3—H3A118.2C13—C12—C11120.5 (4)
C4—C3—H3A118.2C13—C12—H12A119.7
C5—C4—C3118.6 (3)C11—C12—H12A119.7
C5—C4—H4A120.7C12—C13—C8121.3 (4)
C3—C4—H4A120.7C12—C13—H13A119.3
C4—C5—C1118.7 (3)C8—C13—H13A119.3
C4—C5—C6119.0 (3)O2—C14—H14A109.5
C1—C5—C6122.3 (3)O2—C14—H14B109.5
O1—C6—N2124.1 (3)H14A—C14—H14B109.5
O1—C6—C5120.0 (3)O2—C14—H14C109.5
N2—C6—C5115.9 (3)H14A—C14—H14C109.5
N3—C7—C8123.1 (3)H14B—C14—H14C109.5
N3—C7—H7A118.4H3WB—O3—H3WA114.0
C6—N2—N3—C7173.6 (4)N2—N3—C7—C8−179.1 (4)
C3—N1—C2—C10.6 (6)N3—C7—C8—C90.2 (6)
C5—C1—C2—N1−0.8 (6)N3—C7—C8—C13−179.3 (4)
C2—N1—C3—C40.3 (6)C13—C8—C9—C10−1.0 (6)
N1—C3—C4—C5−1.0 (6)C7—C8—C9—C10179.5 (4)
C3—C4—C5—C10.8 (5)C8—C9—C10—C110.6 (6)
C3—C4—C5—C6−178.8 (4)C14—O2—C11—C12−173.3 (4)
C2—C1—C5—C40.1 (5)C14—O2—C11—C106.2 (7)
C2—C1—C5—C6179.6 (3)C9—C10—C11—O2−178.5 (4)
N3—N2—C6—O1−1.1 (6)C9—C10—C11—C121.0 (6)
N3—N2—C6—C5−180.0 (3)O2—C11—C12—C13177.3 (4)
C4—C5—C6—O1−37.8 (5)C10—C11—C12—C13−2.2 (6)
C1—C5—C6—O1142.7 (4)C11—C12—C13—C81.8 (6)
C4—C5—C6—N2141.0 (4)C9—C8—C13—C12−0.2 (6)
C1—C5—C6—N2−38.5 (5)C7—C8—C13—C12179.3 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···O30.862.132.957 (4)162
O3—H3WB···O1i0.961.962.889 (4)161
O3—H3WA···N1ii0.991.922.901 (4)170
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1/2, −y+1, z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···O30.862.132.957 (4)162
O3—H3WB···O1i0.961.962.889 (4)161
O3—H3WA···N1ii0.991.922.901 (4)170
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1/2, −y+1, z+1/2.
Acknowledgements top

The authors are grateful for financial support from the National Natural Science Foundation of China (grant Nos. 20431010 and 20171012).

references
References top

Jing, Z.-L., Fan, Z., Yu, M., Chen, X. & Deng, Q.-L. (2005). Acta Cryst. E61, o3208–o3209.

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McArdle, P. (1995). J. Appl. Cryst. 28, 65–?.

Molecular Structure Corporation (1999). TEXRAY (Version 1.10) and TEXSAN (Version 1.10). MSC, The Woodlands, Texas, USA.

Qiu, X.-Y., Xu, H.-J., Liu, W.-S. & Zhu, H.-L. (2006). Acta Cryst. E62, o2304–o2305.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Yang, S., Zhang, S.-P., Wu, Y.-Y. & Shao, S.-C. (2006). Acta Cryst. E62, o28–o30.

Yin, H.-D., Hong, M., Xu, H.-L., Gao, Z.-J., Li, G. & Wang, D.-Q. (2005). Eur. J. Inorg. Chem. pp. 4572–4581.